CN102939150A

CN102939150A - Method and apparatus for monitoring and restoring electrical properties of polymerization reactor wall film

Info

Publication number: CN102939150A
Application number: CN2011800263586A
Authority: CN
Inventors: E·L·玛科尔; W·A·兰伯蒂; H·W·德克曼
Original assignee: Univation Technologies LLC
Current assignee: Univation Technologies LLC
Priority date: 2010-05-28
Filing date: 2011-05-20
Publication date: 2013-02-20
Anticipated expiration: 2031-05-20
Also published as: WO2011149769A1; CN102939150B; EP2576042A1; EP2576042B1; US20130116391A1; RU2542240C2; RU2012157626A; BR112012030116A2; US8722818B2

Abstract

Described herein are methods for monitoring and restoring electrical properties of polymerization reactor wall films. The method may comprise using a reactor wall monitor to monitor and determine an electrical property, such as the bed voltage or breakdown voltage, of the wall film. The method may further comprise adding continuity additive to the reactor and/or adjusting the feed rate of continuity additive being added to the reactor in response to the measured electrical property.

Description

Monitor and recover the method and apparatus of the electrical properties of polymerisation wall film

Background technology

Conventional fluidized-bed polymerization reactor may " be tied sheet (sheet) " in the wall formation of reaction vessel easily.The knot sheet refers on the resin of melting and the wall or dome that resin particle is attached to reactor.Between the existence of excessive electrostatic charge correlation is arranged in reactor knot sheet and the reactor between polymerization period.The temperature deviation at the unexpected variation thing followed reactor wall place by the static level can prove this point.When the electrostatic charge level on catalyst and the resin particle surpassed certain level, electrostatic force was driven to these particulates on the grounded metal wall of reactor.These particulates reside in and have promoted on the reactor wall because fusing and the particulate melting that heats up causes disintegrating of fluidisation pattern.

Exist polymer coating on the bed wall of gas phase (fluid bed) polymer reactor and can reduce the trend that reactor forms the knot sheet.If there is not theoretical constraint, think that then the triboelectric charge that originally can occur when the existence of reactor wall coating has suppressed resin friction reactor metal wall in the fluid bed shifts, this thereby minimized (or reducing) electrostatic charges accumulated on the resin.Such polymer film coating is as insulating barrier, and it has reduced the electrostatic charge in the reactor assembly, thereby has reduced the possibility of knot sheet during the normal polymerisation.Think between polymerization period in the bed that the electrostatic charge of polymer (such as polyethylene) resin is subject between polymer wall film and the reactor/recyclegas the mutually strong effect of electro ultrafiltration, therefore is subject to the strong effect of the electric characteristic of polymer wall film.For example, thick insulation wall film can limit electric charge from bed polymer to the earth transmission.

When the polymer coating on the bed wall is in " well " state, as indicated in its electric charge Decline traits (such as breakdown voltage), for a long time (several months or several years) operation of fluid bed and do not have excessive static and not have owing to tie the operation problem that sheet causes.But, when the polymer wall coating is in " bad " state, may progressively form the static activity of a great deal of in fluid bed, it often causes tying sheet.

Along with passage of time, described polymer coating may degenerate or become contaminated.For example, deposit the result on it as erosion and/or impurity (such as the catabolite of alkyl aluminum), they may be degenerated.Such degeneration and/or pollution may have significant impact to the operability of described reactor.Conventional method is to carry out when needed reactor assembly to process to remove bed wall coating degeneration or contaminated again and substitute it with new polymer coating.The Retreatment method of routine comprises that described bed wall is prepared (in typical case by removing existing bad polymer coating) and the new polymer coating of original place generation on described wall.For example, can use conventional Retreatment method, process or hydro-blasting such as two luxuriant chromium.Wall is processed costliness again and need to be closed described reactor for described the processing again.Therefore, what may expect is the reliable method attitude that has for the shape that monitors existing bed wall coating during the converging operationJu Hecaozuo of reactor, when does not need as judging when to need to process again.

In the past, the polymer coating on the bed wall of described fluidized-bed polymerization reactor is to look for chance (when described reactor is closed) by the personnel inspection that enters in person described reaction vessel with suitable inspection apparatus in typical case.As an alternative, conventional metal testing plate method is used for checking coating, but this technology has to carry out with off-line mode under the condition that not necessarily represents the actual motion condition.So, need to have during polymerisation is carried out in reactor (as the probe that uses the reactor outside between each stage of reaction with on-line mode) monitor the method for polymer coating on the bed wall of fluidized-bed polymerization reactor as described in (as checking and/or feature is described) (whether degenerated or become contaminated such as the assessment coating).In addition, process for two luxuriant chromium expensive and consuming time or hydro-blasting, the method for not closing reactor and recovering the wall film quality need to be arranged.

Summary of the invention

Herein disclosed is the method for olefin polymerization, comprise: (a) during polymerisation, use at least one electrostatic probe in the fluidized bed reactor system to monitor coating, coating comprises the distal portions of every described electrostatic probe and the lip-deep polymer film of described reactor assembly, wherein said coating is exposed to described intrasystem streaming flow, to determine at least one electrical properties of described coating; (b) the described electrical properties that will in step (a), determine and the contrast of the reference breakdown voltage of described coating; And if (c) described with reference to breakdown voltage less than described coating of described electrical properties, then increase continuous adding agent a period of time to polymer reactor, until described with reference to breakdown voltage more than or equal to described coating of the determined electrical properties of described coating.The described supervision of described coating can comprise: (i) during the very first time interval between the stage of reaction described in the described reactor assembly, operate described electrostatic probe indicates the foaming in the described fluid bed with generation high-speed data; And at least one electrical properties of (ii) determining described coating from described high-speed data.

Description of drawings

Fig. 1 is the simplification cross-sectional view of reaction system, comprises fluidized-bed reactor 4, has the electrostatic probe assembly 2 of installing for the coated bed wall that monitors reactor 4, and the electrostatic probe assembly 2 ' for monitoring that coated recycle gas line 11 is installed;

Fig. 2 is the simplification enlarged cross sectional view of a part of the bed wall 20 of reactor 4 among the probe 3 of assembly 2 among Fig. 1 and Fig. 1, has the block diagram of assembly 2 other elements;

Fig. 3 is the figure that monitors during the bed wall of reactor 4 by electrostatic probe assembly 2 data that produce of Fig. 1;

Fig. 4 is simplification, the side-looking cross-sectional view of a part that is installed to the difunctional electrostatic probe of displaying of reactor beds wall;

Fig. 5 is the simple version that Fig. 4 dwindles, with the block diagram of the add ons of difunctional electrostatic probe;

Fig. 6 be when the reactor discontinuous operation in the example during polymerisation by the figure of data that electrostatic probe produces;

Fig. 7 be to reactor added continuity auxiliary after in the example during polymerisation by the figure of electrostatic probe produces data.

The specific embodiment

Before disclosing and introducing current compound, parts, component, device, software, hardware, equipment, configuration, schematic diagram, system and/or method, be to be understood that, unless show in addition, the invention is not restricted to specific compound, parts, component, device, software, hardware, equipment, configuration, schematic diagram, system, method etc., therefore can change, unless otherwise.It is also understood that term used herein only is to be not intended to limit for specific embodiment is described.

Must be pointed out that also as used in specification and subsidiary claims, " a " of singulative, " an " and " the " comprise plural the denotion unless otherwise.

During reaction " online " of data expression of producing (perhaps carrying out another operation) refers to that the generation (perhaps carrying out other operations) of data is enough rapid herein so that these data (or the result who operates) in essence immediately or the some time afterwards be used between the stage of reaction and use.The during reaction expression of " data with on-line mode produce " is used with the free burial ground for the destitute with the during reaction expression of the online generation of data.If laboratory tests have expended the too many time, so that may change significantly in the time durations response parameter of implementing this test and needing, then the generation data are not regarded as during reaction the data of " online generation " from (at least a material that adopts reaction or produce) laboratory tests.The online generation of having imagined data can comprise uses the previous database that produces, and it can produce with any of various mode, comprises laboratory tests consuming time.

About the product that is produced by successive reaction, the expression of " instantaneous " value of product property is herein representing the numerical value of the character of the up-to-date production quantity of this product.Because the back-mixing character of gas-phase polymerization reactor, the polymeric articles of up-to-date production experiences first and the mixing of the product volume of previous production in typical case, recently and the previous product mixture of producing leave again reactor.In contrast, about the product of being produced by successive reaction, the expression of herein " on average " of certain character (at time " T ") (or " bed on average ") value is illustrated in the numerical value of character that time T is left the product of reactor.

The expression of " polyethylene " represents ethene and one or more C alternatively ₃-C ₁₀At least a polymer of alhpa olefin, and polyolefinic expression represents one or more C ₃-C ₁₀At least a polymer (or copolymer) of alhpa olefin.

The disclosure from start to finish, the abbreviation " MI " all represent melt index.The same disclosure from start to finish, the intrinsic material density of term " density " expression polymeric articles (take g/cc as unit, unless otherwise regulation) is measured according to ASTM-D-1505-98, unless regulation otherwise.

Herein, certain probe represents that this probe is configured and is installed as the operating period that monitors reaction or reactor at probe, the polymerisation of neither significantly disturbing also not appreciable impact to occur in the expression of reactor " outside " (or " outside " probe) in reactor.For example, if in order to monitor that the voltage in this (or produces the bed voltage data, it is used to monitor the film of the distal portions that applies this wall and this probe), during reaction when this probe operation, this probe had both disturbed the polymerisation that does not also otherwise affect significantly in the reactor indistinctively, and then flushing or slightly extend to probe this, that have distal portions (such as the tip) from the bed wall with the bed wall of reactor can be " outside " probe.

Herein, the electrostatic charge that produced by the CONTACT WITH FRICTION of the inclusion that relates to fluidized-bed polymerization reactor (such as fluoropolymer resin) of " bed static " expression (and/or because the current potential of charge generation).For example, bed static can be derived from fluoropolymer resin in the bed and the CONTACT WITH FRICTION of reactor beds wall (wall in the fluid bed section of reactor).Use the probe of reactor outside to monitor that reactor beds static is conventional way.For example 6,008,662 and 6,905, introduced the electrostatic probe that is suitable for measuring a static in No. 654 United States Patent (USP)s.

Just as used herein, " biofilm formed on wall of reactor monitor " introduced a kind of method, be used in the coating of using at least one electrostatic probe supervision during fluidized bed reactor system (being sometimes referred to as " reactor " in order the to make things convenient for this paper) polymerisation on the distal portions of the surface of reactor assembly and every electrostatic probe, wherein this coating this method the term of execution be exposed to streaming flow in the reactor assembly.In typical case, this surface is the bed wall (being exposed to the wall of reactor fluidisation bed) of reactor, and this coating during reaction is exposed to (as the bubbling) fluid that flows in the fluid bed.In typical case, every electrostatic probe all is the external probe (as directly being installed to reactor) of installing, and its distal portions flushes with the reactor beds wall or slightly extends to the fluid bed from this wall.In typical case, this coating is the film that had been precoated on the polymer on the distal portions of a wall and every probe before carrying out reaction (such as thickness less than 0.50 millimeter or in about 0.025 to 0.50 millimeter scope).

The method that this paper introduces is used for monitoring and recovering the electrical properties of biofilm formed on wall of reactor.This method can comprise the electrical properties of using the reactor wall monitor to monitor and determine the wall film, such as bed voltage or breakdown voltage.This method may further include in response to measured electrical properties, adds the continuous adding agent to reactor, and/or adjusts the feed rate of the continuous adding agent of forward reaction device interpolation.For example, if the breakdown voltage of measured wall film has dropped on below the predetermined reference value, so just can add the continuous adding agent to reactor, and/or can increase the feed rate of the continuous adding agent of forward reaction device interpolation.In another example, if the breakdown voltage of measured wall film more than predetermined reference value, so just can reduce or stop the feed rate of the continuous adding agent of forward reaction device interpolation.

Introduce the example of polymerization reactor system with reference to Fig. 1, can monitor and also control alternatively its operation.The system of Fig. 1 comprises fluidized-bed polymerization reactor 4.Reactor 4 has top expansion (i.e. " dome ") section, and it comprises the cylinder changeover portion of reactor and the end section between the section of the cylinder (directly) between hemispherical top head, dispenser panel 10, plate 10 and the top expansion segment, gas access pipeline 11 and gas access pipeline 11 and the dispenser panel 10.The fluid bed 1 of granular polymer and catalyst particles is comprised in the straight section.Make this fluidisation from suction line 11 via the steady flow of the recycle gas of dispenser panel 10.Bubble 1A moves through bed 1 during typical converging operationJu Hecaozuo.In order to provide mixing relatively good fluid bed, adjust the flow velocity of fluidizing gas, as showing among the figure.

Reactor assembly also has catalyst dispenser (not shown), is used for polymerization catalyst to the controlled interpolation of fluidized bed reaction zone.In reaction zone (being fluid bed), catalyst particles and ethene, comonomer and optional hydrogen and other reacting gas react to produce the granular polymer particulate.Along with the generation of new polymer particles, other polymer particles are discharged system 20 via product continuously and are taken out from fluid bed.After polymer particles has passed through product discharge system, flow degassed (or " purification ") in order to remove the hydrocarbon materials of basically all dissolving with inert nitrogen.

The reactor assembly of Fig. 1 also has the cooling control loop, and it comprises recycle gas pipeline 13, compressor 6 and recyclegas cooler 12, couples with reactor 4, as shown in the figure.At run duration, flow to reactor 4 from the recyclegas (it may contain the liquid of condensation) of the cooling of cooler 12 via suction line 11, then upwards propagate via this bed and via outlet 15 from reactor 4 out.Under the preferable case, cooler 12 is positioned in the downstream (as shown in Figure 1) of compressor 6, but also can be positioned in certain embodiments the upstream of compressor 6.

Expansion segment is also referred to as " Speed Reduction district " or " abscission zone ", and is designed to make the particulate loading of taking away from fluid bed to minimize.The diameter of each horizontal slice of expansion segment is greater than the diameter of straight section.The diameter that increases causes the Speed Reduction of fluidizing gas, this resin particle that allows great majority be pulled away precipitates back in the fluid bed, thereby the solid particle amount of taking away (or " transporting ") from (at the set-point of fluidization gas velocity) fluid bed via recycle gas pipeline 13 is minimized.

Each comprises probe 3 one or more electrostatic probe assembly 2() be arranged to monitor that the coating 21(on the bed wall 20 of reactor 4 is presented among Fig. 2 rather than Fig. 1).Bed wall 20 is reactor 4 is exposed to fluid bed 1 during polymerisation inner wall section.In typical case, coating 21 is before the normal converging operationJu Hecaozuo of reactor assembly, and the distal portions (tip) with probe 3 on bed wall 20 is coated with the polymer coating of (as processing by two luxuriant chromium).Every probe 3 all has distal portions, slightly protrudes in the fluid bed 1, is exposed to fluid bed 1 but perhaps flush with the bed wall 20 of reactor 4.Only shown for simplicity an electrostatic probe assembly 2, but other can be installed in other positions on the wall 20.

What each of one or more electrostatic probe assemblies 2 ' (each comprises probe 3 ') was arranged to system in the watch circle 1 takes away the lip-deep coating in district.Shown such assembly 2 ' among Fig. 1, the distal portions of its probe 3 ' flushes with the wall of suction line 11, and is exposed to the fluid that flows through pipeline 11.As an alternative, probe 3 ' has the distal portions that slightly protrudes inlet pipe line 11 inside.The film 11A of coating pipeline 11 inner surfaces also is coated on the distal portions of probe 3 '.The coating 11A of (on the distal portions of probe 3 ') is exposed to the fluid that flows through pipeline 11 on the pipeline 11.Only shown for simplicity an electrostatic probe assembly 2 ', but other the system among Fig. 1 of can being installed in take away other positions in the district.

Other sensors such as the bed tempertaure sensor, are arranged in fluid bed in typical case, and use with control system (among Fig. 1 show) and the external refrigeration loop that is couple to heat exchanger 12, to control the fluidized-bed temperature Trx of close technique set-point.The gas reactor of relative warmth (it has obtained the temperature that basically equates with fluidized-bed temperature during it flows through reactor 4) is removed and pumps into cooler 12 by compressor 6 from exporting 15, and wherein the temperature of gas (cooling fluid) is lowered.Relatively cold fluid (it may comprise the liquid of condensation) flows out to reactor inlet so that cooling bed from cooler 12.Temperature sensor (not shown) near cooler 12 entrance and exits provides feedback to control system, and the fluid that enters reactor to adjust 12 pairs in cooler reduces the amount of temperature.

The system of Fig. 1 can also comprise many skin temperature sensors (being embodied as in typical case the thermocouple sensor with rapid response design), be installed in along some positions of reactor wall straight section (and also being alternatively the tapered segment of expansion segment), so that from outstanding certain short distance (such as 3 to 12 millimeters) to reactor of wall.These sensors are configured and are arranged as the sensing run duration near the resin of the wall of reactor 4 and/or the temperature T of gas reactor _w

Other sensors and also alternatively other devices also be used in typical case other response parameters of measuring during the polymerisation.Comprise the instantaneous naval stores character average with bed (such as melt index and the density of the fluoropolymer resin product produced by system among Fig. 1 during the polymerisation) under other response parameter preferable case like this.The general measure mode of the naval stores character that bed is average to its sample termly (as per hour once), and is carried out suitable test for when resin leaves reactor in the quality control laboratory.The routine of instantaneous product property determines that mode is based on (well known in the art) computational methods to the specific reaction model of employed concrete catalyst.Reaction model in typical case gas phase cocnentration factor (such as the molar ratio of 1-hexene/ethene and the molar ratio of hydrogen/ethene) and the polymer of producing moment density and melt index be associated.

Comprise the gas reactor component under other response parameter preferable case of measuring, such as total overall reaction thing gas and induced condensing agent (ICA), and the concentration (and dividing potential drop) of the whole inert gases (such as nitrogen, inert hydrocarbon etc.) that exist with relevant quantity.The gas reactor component can be measured with gas chromatography systems.

How to have known the adjusting process variable, the a plurality of homeostatic reactions that undertaken by system among Fig. 1 with control (such as concentration and the dividing potential drop of at least a reactant (such as ethene), the type that is incorporated into every kind of catalyst in the reactor 4 and the character of control gas phase component, induced condensing agent (ICA), and use

element

6 and 12 control temperature in the mode of introducing above).

Fig. 2 is the simplification enlarged drawing of assembly 2 among Fig. 1.As shown in the figure, polymer thin coating 21(film) the bed wall 20 of reactor 4 and the distal surface of probe 3 have been applied.In general, elongate cylinder probe 3 is installed to be its coated distal surface and flushes with the inner surface (left surface among Fig. 2) of bed wall 20, so that the coated distal surface of probe 3 is exposed to fluid bed during reaction is carried out.Mounting flange 22 is outstanding from the outer surface of wall 20 around the near-end of the passage (by wall 20) that is used for reception probe 3.Shell 24(partly shows) comprise the major part of assembly 2, and preventing fluid, reveals from fluid bed the Fluid Sealing 23 between shell 24, flange 22 and probe 3.

Probe 3 comprises Metallic rod 9, and the electrically insulating material 8 that centers on bar 9 cylindrical side surfaces.DC current flows between insulating materials 8 anti-stopping bars 9 and conduction (metal) wall 20, the mouth of pipe 22 and the shell 24.

Thereby assembly 2 also comprises the coated distal surface that is coupled in probe 3(probe 3) and the earth between electrometer 7.Electrometer 7(such as ammeter or voltmeter) have in typical case very high resistance and be grounding to wall 20 self.

Electrometer 7 is used to monitor the reading from probe 3.Processor 5 is connected to electrometer 7 with the output sampling to electrometer 7, and sampled data is carried out necessary processing, in order to determine at least one electrical properties of coating 21.In typical enforcement, electrometer 7 is can measure at the tip of probe 3 instrument or the equipment of the current flowing of geoinduction, and can be (for example) ammeter, picoammeter (high sensitivity ammeter) or universal meter.The electric current of responding in the tip of probe 3 can also be determined by the voltage that resistor produces by this electric current indirectly by measuring.

Under the preferable case, processor 5 is programmed and otherwise is configured to the output sampling to electrometer 7, and sampled data is carried out necessary processing, determines at least one electrical properties of coating 21 with on-line mode.The electrical properties of determining with on-line mode can be used in typical case controlling described reaction and does not have bad delay.For example, the electric parameter of determining with on-line mode can be used for triggering the change of relevant response parameter, in addition trigger reactor close (as for fear of otherwise the excessive state of emergency of resin viscosity in the reactor).

The key element 3 ' of Fig. 1 middle probe assembly 2 ', 5 ' and the 7 ' element 3 corresponding to (and can be same as)

probe assembly

2,5 and 7.It is identical with assembly 2 that assembly 2 ' can be embodied as, but the coated distal surface that is installed in probe 3 ' flushes (rather than as the probe 3 of assembly 2 coated inner surface at bed wall 20) with the coated inner surface of pipeline 11

Coating on the bed wall of fluidized-bed polymerization reactor system (polymer film 21 in such as Fig. 1 on the bed wall 20), perhaps the character of taking away the lip-deep coating in district (such as the coating 11A on the pipeline 11 of system among Fig. 1) of fluidized-bed polymerization reactor system can use rapid data collection and analytical method to determine.The inventor has realized that high-frequency electrostatic signal (such as the electrostatic data by with the sample frequency of 100Hz the output of electrostatic probe being sampled and produced) is arranged by inductance when the process of the bubble in fluid bed electrostatic probe.Bubble so that without electric charge through probe, and in probe, induce electric current by Gauss law.The characteristic frequency of electrostatic pulse is less than the characteristic frequency of the high-speed data of (using at least one electrostatic probe) generation and employing in order to monitor a wall coating performance.Getted over and the characteristic frequency of the electrostatic pulse responded to is in a typical case relatively low (such as the run duration at the fluidized-bed polyethylene polymer reactor by bubble, from about 2Hz to about 6Hz, perhaps from 1Hz to about 10Hz) scope (this paper is referred to as " foaming frequency range " sometimes) in.For in describing bed wall coating feature, using the high-speed data that produces to have frequency component in the foaming frequency range.For example, has frequency component in the foaming frequency range by the high-speed data that the output sampling of electrostatic probe is produced with the sample frequency (such as the sample frequency of 100Hz, the frequency range of wherein bubbling is from 2Hz to 6Hz) of at least twice of the highest frequency of foaming frequency range.

Because the foaming in the fluid bed is determined by some factors by the high speed AC signal that electrostatic probe produces, and comprises bubble size and bubble velocity, and near the mean charge on the fluoropolymer resin this probe.In exemplary embodiments, polymerisation is carried out under the typical close limit running status in commercial reactors, supposes that the variation of average bubble size and average bubble velocity can be ignored.After this hypothesis of making, just obtained useful result.

Perhaps, Ohm's law is the simplest description to the electrical properties of material, and is the starting point of understanding bed wall film character.If the electric current by simple conductor, is just said this conductor along with the voltage linear ground of striding this conductor increases and is obeyed Ohm's law.Semiconductor and insulator are not observed Ohm's law.

The process useful of determining the electrical properties of coating on the polymer reactor bed wall is each time (in each window such as a series of time windows) (from the high-speed data that uses at least one electrostatic probe to produce) of a series of times during the polymerisation in reactor to determine following two amounts:

Current potential in the fluid bed (because this amount is confirmed as the coated distal portions of probe and the voltage between the earth in typical case, so this amount will be called as " bed voltage " in this article sometimes); And

Via the electric current of the coated distal portions of probe from this to the earth (such as the average current of being responded in probe by the electric charge in the fluid bed at the correlation time window, the distal portions coated by probe extracts the earth).

Various different modes of introducing with this paper any, can both determine that the bed magnitude of voltage is (such as standard deviation, covariance value or the cross correlation value from being determined by high-speed data from the high-speed data of measuring, the perhaps mean power from being extracted in the correlated frequency scope by probe is as using Fourier or wavelet method or causing the another kind of method of noise testing to be determined from high-speed data).

The bed magnitude of voltage can contrast current value and draw.Fig. 3 is the example of such figure, and wherein each graphical pointv represents during the polymerisation bed voltage during different in a series of time windows one and the probe current of induction.Or rather, each graphical pointv is illustrated in window correlation time along the position of the longitudinal axis, the average current of being responded in probe (such as the probe 3 of Fig. 1 and Fig. 2) by the electric charge in the fluid bed.This electric current is extracted to the earth by the coated distal portions of probe from fluid bed, measured in the reasonable time interval (such as the electrometer 7 by Fig. 2), sampling and average (such as the processor 5 by Fig. 2) and with arbitrary unit drawn (in Fig. 3).Each graphical pointv is illustrated in the average bed voltage between window phase correlation time along the position of Fig. 3 transverse axis, and with arbitrary unit.

Fig. 3 has shown the curve to the drawing point match.Just as apparent from Figure 3, a bed voltage (this paper is called " breakdown voltage " of coating on probe distal part and the bed wall) is arranged, this curve is linear (having positive slope) during greater than it.Breakdown voltage is about 0.33 unit of a voltage in Fig. 3.Under the bed voltage status greater than breakdown voltage, bed wall coating has the electrical properties (it observes Ohm's law) of conductor.Under the bed voltage status less than breakdown voltage, bed wall coating has the electrical properties (it does not observe Ohm's law) of insulator.

In several weeks, several months and the several years of reactor operation, the breakdown voltage of bed wall coating and the electric conductivity after the puncture will develop in typical case.For example, observed breakdown voltage raising after using the metalloscene catalyst polymerization to produce high MI polyethylene grade.Also observe the very slowly differentiation of the wall rete in reactor " is taken away the district " (such as the lip-deep rete of recycle gas line) of (as in a few days and several weeks) variation, might be owing to clean through the low dynamics of particulate.

The biofilm formed on wall of reactor monitor can use at least one electrostatic probe (such as probe 3 or the probe 3 ' of Fig. 1) to monitor coating on the distal portions of the surface of reactor assembly and every electrostatic probe in fluidized-bed polymerization reactor system (being sometimes referred to as " reactor " in order to make things convenient for this paper) during the polymerisation, wherein this coating this method the term of execution be exposed to streaming flow in the reactor assembly.In typical case, this surface is that bed wall (such as the bed wall 20 of Fig. 2) and this coating (such as the coating 21 of Fig. 2) that is exposed to the reactor of reactor fluidisation bed during reaction is exposed to (as the bubbling) fluid that flows in the fluid bed.In typical case, every electrostatic probe all is external probe, when (as directly being installed to reactor) is installed its distal portions is flushed with the reactor beds wall or slightly extends to the fluid bed from this wall.In typical case, this coating is the film (such as thickness in about 0.025 to 0.50 millimeter scope) of polymer, has been coated in advance on the distal portions of a wall and every probe before carrying out reaction.That this method may further comprise the steps among the embodiment on the distal portions (such as the distal surface of Fig. 2 middle probe 3) of and every electrostatic probe upper at reactor beds wall (such as the bed wall 20 of Fig. 2) in the coating that will be monitored (such as the coating 21 of Fig. 2):

(a) in reactor, carry out operating this electrostatic probe to produce a series of data values (this paper is referred to as " high-speed data " sometimes) during the very first time interval between the stage of reaction, indicate the foaming in the fluid bed.High-speed data comprise in typical case from about 1Hz to about 10Hz or from about 2Hz to about 6Hz scope the frequency component in (" foaming frequency range "), and the duration in the first interval be a few minutes in typical case; And

(b) determine at least one electrical properties (such as at least one electrical properties of last minute coating of electrostatic probe distal portions) of this coating from high-speed data.

(for every electrostatic probe) foaming frequency range is to be moved the frequency range of the signal of telecommunication of responding in this electrostatic probe for electrostatic probe by the bubble phase in the fluid bed.In certain embodiments, determined independently the foaming frequency range (as be confirmed as be with the bandwidth of its bed DP reading that similarly produces during reaction or the polymerisation, wherein each DP reading is that the instantaneous pressure measured between fluid bed bottom and the top is poor), and each described electrical properties of this coating in step (b) from meeting or comprising the frequency component of the high-speed data in the scope of the independent foaming frequency range of determining and producing.In certain embodiments, by with the sample frequency of 100Hz at least the output of every electrostatic probe being sampled, produce high-speed data.

Under the preferable case, at least one electrical properties of determining in step (b) is the breakdown voltage of this coating.In certain embodiments, this method is further comprising the steps of:

(c) pollution level of determining the degree of degeneration of this coating and this coating from least one electrical properties of determining step (b) is one at least.For example, step (c) can comprise that from the electrostatic probe distal portions of determining the breakdown voltage of coating determines the step of this coating degradation degree.

During reaction can be with on-line mode execution in step (a) and (b) (perhaps step (a) and (b) and (c) whole).

In certain embodiments, this method has also comprised the step of processing again that judges whether to carry out this surface step (b) from least one electrical properties of determining, as remove this coating (becomeing contaminated to enough degree as having degenerated or become because of it) and replace it with new coating, perhaps otherwise on this surface, again create useful coating (as by using continuous auxiliary agent to precipitate coating material on this surface).In certain embodiments, at least one electrical properties of determining in step (b) is or defines at least information of the feature of one of state that land used describes the mechanism of state of charge in this, charge generation, the fluidisation in the reactor and coating.

In certain embodiments, very first time interval comprises one group of subinterval, and step (b) may further comprise the steps:

The difference that settles the standard, mode is for each subinterval in the group of subinterval, from the high-speed data that produces described each subinterval in the first interval, determines the standard deviation of the high-speed data that produces in the subinterval; And

From high-speed data and standard deviation, determine the current potential in the fluid bed during described each subinterval in the first interval.For example, the processor 5 of Fig. 2 is programmed to determine such standard deviation from the sampling of electrometer 7 output, and determines current potential the fluid bed from such standard deviation and sampling output data.

In other embodiments, very first time interval comprises one group of subinterval, high-speed data indicates during described each subinterval in the first interval, the mean power that (owing to the electric current of being responded in this probe by the electric charge in the fluid bed) extracted by this probe, and step (b) may further comprise the steps:

Determine the current potential the fluid bed during described each subinterval in the first interval from high-speed data.For example, the processor 5 of Fig. 2 is programmed to determine such average power content from the sampling of electrometer 7 output, and determines current potential the fluid bed from such value and sampling output data.In certain embodiments, used Fourier or wavelet method, perhaps used the another kind of method that causes noise testing, with the mean power of determining to be extracted in the correlated frequency scope by this probe.

In certain embodiments, very first time interval comprises one group of subinterval, and step (b) has comprised the step that produces the average data value from high-speed data, mode is for each subinterval in the group of subinterval, the average high-speed data that in described each subinterval, produces, and from average data value and high-speed data, determine at least one described electrical properties of this coating.

In another kind of embodiment, very first time interval comprises one group of subinterval, and step (b) may further comprise the steps:

Determine cross-correlation (such as auto-correlation) value, mode is described each subinterval for the first interval, determines the cross-correlation of one of version after the processing of the described high-speed data that produces in the described high-speed data that produces in the high-speed data that produces in this subinterval and this subinterval and this subinterval; And

Determine the current potential the fluid bed during described each subinterval in the first interval from high-speed data and cross correlation value.For example, the processor 5 of Fig. 2 is programmed to determine such cross correlation value from the sampling of electrometer 7 output, and determines current potential the fluid bed from such cross correlation value and sampling output data.

This cross correlation value indicates the movement of this probe of bubble process in the fluid bed.For example, when cross correlation value drawn (being that voltage is to the time), can determine the displacement voltage that indicated by data value, wherein each such " displacement voltage " comprises that peak value (the highest) voltage is rear succeeded by minimum voltage in time delay (as in 0.5 to 2 second scope), and perhaps minimum voltage (after the time delay of same range as) is succeeded by ceiling voltage.In this example, the mode that will introduce with this paper is determined the relative measurement (distal portions that this probe the is coated and voltage between the earth) of bed static from this displacement voltage.

Among some embodiment of kind, the function " xcorr " in the Matlab software that use (MathWorks produces) can be bought is carried out cross-correlation calculation in the back.As an alternative, carry out cross-correlation calculation in computer or other treatment systems (such as the processor 5 of Fig. 2) with another kind of appropriate ways programming.In order to use Matlab software to calculate the cross-correlation of (having comparable size) vector x and y, fill order in the environment of Matlab " output=xcorr(x, y) ".Carry out vector x and the auto-correlation of himself as special circumstances utility command " output=xcorr(x) ".

For example, during carrying out polymerisation, the high speed electrostatic data of collecting five minutes by operating (Fig. 2's) processor 5 is sampled to the output of (the electrostatic probe assembly of Fig. 2) electrometer 7 with the sample frequency of 100Hz, thereby produced the vector of 30,000 data values.Cross-correlation is carried out in the following manner, in order to determine coated distal portions and the voltage between the earth (it is regarded as the measurement of the current potential in the fluid bed) of probe:

(i) from data value, remove zero offset and baseline drift (as using " detrend " function of Matlab software) to determine the vector of trend;

(ii) determine the absolute value of the vector data value of trend, thereby determine the vector of absolute value;

(iii) vector that goes trend and the vector of absolute value are carried out cross-correlation, thereby determine cross-correlation vector.

This cross-correlation vector indicates the movement of this probe of bubble process in the fluid bed.For example, when the data value of cross-correlation vector drawn (being that voltage is to the time), definite " displacement voltage " that is indicated by data value, wherein each such " displacement voltage " comprises that peak value (the highest) voltage is rear succeeded by minimum voltage in time delay (in 0.5 to 2 second scope), and perhaps minimum voltage (after the time delay of same range as) is succeeded by ceiling voltage.This, scope was used for having the typical polymerization reaction of typical superficial gas velocity time delay.In general, suitable scope time delay depends on the superficial gas velocity in reactor.

Covariance is the well-known parameter relevant with cross-correlation.Determine in certain embodiments of the present invention covariance value rather than cross correlation value.Therefore, in certain embodiments, very first time interval comprises one group of subinterval, and step (b) may further comprise the steps:

Determine covariance value, mode is described each subinterval for the first interval, determines the covariance of one of version after the processing of the described high-speed data that produces in the described high-speed data that produces in the high-speed data that produces in this subinterval and this subinterval and this subinterval; And

Determine the current potential the fluid bed during described each subinterval in the first interval from high-speed data and covariance value.

The relative measurement (distal portions that probe the is coated and voltage between the earth) of determining bed static from displacement voltage is as follows.According to each displacement voltage, in the time (such as the time of leading voltage extremity appearance) that displacement voltage occurs, the distal portions that probe is coated and the relative measurement of the voltage between the earth are the amplitudes that the amplitude of the leading voltage extremity (maximum or minimum) of displacement voltage deducts lagging voltage extreme value (maximum or minimum).This method is particularly useful, because kept the symbol of average resin electric charge.

The electrostatic measurement (such as the measurement of introducing in above example) of carrying out will depend on average bed static and fluidisation (bubble size and speed, and the heterogeneity of bed) in typical case.Experience demonstrates, the close limit of the gas velocity of given commercial employing and near dispenser panel (it is being controlled bubble and is forming), the fluidisation behavior is reproducible in the hypomere of typical polymer reactor bed, has determined exactly in typical case the relative measurement of current potential in the hypomere of such fluid bed.In bed the fluidisation in the section may change larger, and depend on consumingly minute bubbles unite to form large and fast bubble.Therefore, determine that the relative measurement possibility of the current potential in the fluid bed epimere is owing to the current potential in fluidisation effect rather than the fluid bed epimere suffers larger uncertainty.

In typical embodiment, this method comprises the sequentially step of the repetition of execution in step (a) and step (b), at every turn execution in step (a) during different time intervals.For example, in some such embodiment, this method is further comprising the steps of:

(c) step (a) afterwards but carry out the second time interval between the stage of reaction in reactor during, the operation of electrostatic probe indicates the foaming in the fluid bed in order to produce additional data value sequence (this paper is referred to as " additional high-speed data ");

(d) determine at least one electrical properties of this coating from additional high-speed data; And

(e) electrical properties determined in step (b) and (d) of response, supervision along with time lapse this coating degeneration and pollute at least one.

In certain embodiments, very first time interval comprises one group of subinterval, the second time interval comprises second group of subinterval, step (b) comprises the step that produces the average data value from high-speed data, mode is each subinterval for the subinterval group, the average high-speed data that in described each subinterval, produces, and determine at least one described electrical properties of this coating from average data value and high-speed data, and step (d) comprises the step that produces additional average data value from additional high-speed data, mode is each subinterval for second group of subinterval, the average additional high-speed data that in described each subinterval, produce, and determine at least one described electrical properties of this coating from additional average data value and additional high-speed data.

In the method for above introduction, can use the polymerisation of difunctional electrostatic probe supervision in fluidized bed reactor system.Difunctional electrostatic probe can comprise:

Insulated probe, the proximal part of the conduction that has the electric insulation distal portions that is configured to during described supervision, be exposed to the streaming flow in the reactor assembly (as the insulation distal portions with distal surface is flushed with bed wall or other reactor surface, perhaps slightly extend to the streaming flow from this reactor surface) and contact with described distal portions; And

The naked probe of conduction, arrange coaxially with insulated probe and have the distal surface that is configured to during described supervision, be exposed to the conduction of the streaming flow in the reactor assembly (as the conduction distal surface is flushed with a wall or other reactor surface, perhaps slightly extend to the streaming flow from this reactor surface).

In typical case, this naked probe is at least basically columniform, and insulated probe is at least basically annular, and the distal surface of naked probe aligns with the distal surface of the insulation distal portions of insulated probe.Under the preferable case, naked probe has side surface, insulated probe has towards the inner surface on naked probe side surface, and difunctional electrostatic probe is included in the electric insulation layer between insulated probe inner surface and the naked probe side surface, is used for making insulated probe and naked probe to insulate.In typical case, insulated probe has the outside layer of electric insulation, is used for making the proximal part of conduction and such element insulating when difunctional electrostatic probe is installed to the conducting element (such as the bed wall) of reactor assembly.

Difunctional electrostatic probe can (under the preferable case simultaneously) be measured the DC current that flows to naked detecting probe surface from the fluid bed of reactor, and flows to the induced-current (between the conducting element of bed and insulated probe directly contacting) of insulated probe from this.In bed same position simultaneously (or basically simultaneously) measure the vital information of feature that these two kinds of effects can provide state to mechanism, fluidisation (via cubic content measurement) and the wall coating that is described in state of charge in this, charge generation (such as deposition, supply, degeneration and the pollution of polymer or wax coating on the naked conduction distal surface of this probe, using from the reading of the insulation distal surface of this probe as a reference).

To introduce the exemplary embodiments of difunctional electrostatic probe 40 with reference to figure 4 and Fig. 5.

As shown in Figure 4, probe 40 comprises:

Insulated probe 46 has the electric insulation distal portions 41(that is configured to be exposed to during use the streaming flow in the reactor distal surface of insulation distal portions 41 is flushed with the bed wall 30 of reactor at least basically) and the proximal part 45 of the conduction that contacts with distal portions 41; And

Conduct electricity naked probe 44, place coaxially with insulated probe, and have be configured to be exposed to during use the conduction distal surface 42(of the streaming flow in the reactor as at least in fact the conduction distal surface is flushed with the bed wall 30 of reactor).

As an alternative, insulation and the distal portions of conducting probe can slightly extend to the streaming flow from this reactor surface (in typical case, double function probe or be installed to reactor elements near this surface).

(Fig. 4 and Fig. 5's) naked probe 44 is columniform basically, and insulated probe 46 is annular basically, and the annular distal end surface in alignment of the insulation distal portions 41 of the distal surface 42 of naked probe 44 and probe 46.Naked probe 44 has the general cylindrical outer surface.Insulated probe 46 has the inner surface that general cylindrical scribbles electric insulation layer 47.During assembling probe 40, layer 47 is towards naked probe 44 and make probe 44 and insulated probe 46 insulation.The outer surface of insulated probe 46 scribbles electric insulation layer 48.When assembling probe 40 and attaching it to reactor beds wall 30, layer 48 is towards wall 30 and make probe 40 and its insulation.

As shown in Figure 5, difunctional electrostatic probe 40 also comprises reading circuit 50, reading circuit 50 be coupled to insulated probe 46 conduction proximal part 45 and be couple to naked probe 44.The output (indicating through the electric current of insulated probe 46 with across the voltage of probe 46 one at least) that circuit 50 is configured to output (indicating through the electric current of naked probe 44 with across the voltage of naked probe 44 one at least) naked probe and insulated probe transmits (assert) to such as data typing and control system.Under the preferable case, circuit 50 is configured to transmit simultaneously the output of naked probe and the output of insulated probe.As an alternative, circuit 50 is configured to sequentially transmit the output of naked probe and the output of insulated probe (such as the mode with time-division multiplex).In the embodiment of Fig. 5, reading circuit 50 are the earth (bed wall 30) with probe 44 and 46 between the ammeter that is connected.More generally, the reading circuit of double function probe of the present invention can be or comprise the proximal part of the conduction that is coupled to insulated probe and be couple to the electrometer (such as ammeter or voltmeter) of naked probe.In typical case, reading circuit is coupled between the proximal part and the earth of conduction of insulated probe during use, and between naked probe and the earth.Reading circuit should present very high resistance to double function probe, is excreted to that process that this sensing element and this probe are designed to measure that affects in order to prevent too many electric charge.Be sent to emitter via screened coaxial cable under the output of reading circuit (being the voltage across very large resistor under the preferable case) preferable case.From the insulation of double function probe of the present invention can be sent to the computer of control system with transmitting of naked probe, be used for record, analysis and control action (as handling continuous auxiliary agent stream).

Double function probe 40 can (under the preferable case simultaneously) be measured the DC current that flows to the distal surface 42 of naked probe 44 from the fluid bed of reactor, and flows to the induced-current (between the conducting element of bed and probe 46 directly contacting) of insulated probe 46 from this.In bed the same position place simultaneously (or basically simultaneously) measure the vital information of feature that these two kinds of effects can provide state to mechanism, fluidisation (via capacitance measurement) and the wall coating that is described in state of charge in this, charge generation (such as deposition, supply, degeneration and the pollution of polymer or wax coating on the naked conduction distal surface of this probe, using from the reading of the insulation distal surface of this probe as a reference).

Because naked probe (such as the probe 44 of Fig. 5) and insulated probe (such as the probe 46 of Fig. 5) all should be measured the same place of (in the fluid bed such as reactor) in the reactor assembly, thus under the preferable case they about each other by coaxially installation (as the embodiment of Fig. 4 and Fig. 5).When double function probe was used for monitoring fluid bed (the perhaps coating on the distal surface of bed wall and insulated probe and naked probe thereof), the insulated probe of double function probe and the distal surface of naked probe should be less than typical bubble sizes in the fluid bed.

The component of (insulated probe 46) electric insulation distal portions 41 may affect uses naked probe 44 determined contact chargings to measure.In some cases, will expect to eliminate this impact or make it to minimize; In other cases, this impact may be desired.Therefore, in some applications, may expect distal portions 41 by triboelectricity matter and during use the material that is complementary of the material (such as the polymer that in fluid bed, is producing) that contacts with it of expection form, so that in the operating period of probe 44 and/or probe 46, eliminate the triboelectric charge of the material contact with distal portions 41 or make it to minimize.As an alternative, also may be desirably in the triboelectricity matter of the material that forms distal portions 41 in other application and expect during use material (such as the polymer that in fluid bed, the is producing) dissmilarity that contacts with part 41, so that in the operating period of probe 44 and/or probe 46, the useful quantity of the triboelectric charge of the material that permission contacts with distal portions 41.

For example,

expection probe

44 and 46 is when polyethylene (" PE ") production period in the fluidized-bed reactor (as shown the reactor of its wall 30 in Fig. 4) operates, may expect to form the distal portions 41 of insulating materials, the PE particulate that its triboelectricity matter and operating period will contact with it is dissimilar.This can allow distal portions 41 make its some PE particulate of operating period contact with the contact electric charge, so that the final electric charge of a part can dissipate by naked probe 44, be that the useful information that the triboelectricity matter of distal portions 41 allows when mating with this PE particulate the output of probe 44 provide can not get possibly.

In order to make the signal strength signal intensity normalization, the area of section of the naked probe of double function probe of the present invention (such as the probe 44 of Fig. 5) and both conducting elements of insulated probe (such as the probe 46 of Fig. 5) can be identical.Under the preferable case, insulated probe is reinforced to guarantee that its insulation distal portions will be not can not be removed because of the fluid of contact reactor system (such as the inclusion of fluid bed) for many years or wear and tear.During wall clean operation (such as sandblast), double function probe of the present invention will probably need to be removed from service, to prevent the damage to the insulation distal portions of its insulated probe.

The exemplary embodiments of double function probe can be used for reading contrast that the reading of traditional (nonisulated) type that electrostatic probe produces and insulation electrostatic probe are produced by the equipment personnel, as for the upper state of shallow layer of confirmatory reaction wall (and each distal portions of nonisulated probe and insulated probe).For example, probe assembly 2(and/or the probe assembly 2 ' of Fig. 1) the present invention that can be implemented as double function probe (type as shown in Figure 5) and be used to carry out this paper introduction monitors any of method.

The exemplary embodiments of double function probe can be used in and monitors the influential device events of bed wall coating.Different polymer grade all may be removed or precipitation polymers in reactor surface (surface that comprises the electrostatic probe that is exposed to fluid bed) with different catalyst, causes the differentiation of wall state.So generation of static electricity and dissipation will develop.Expection (as via on-line monitoring) is more complete and at length understand the wall state and can cause better method to wall management, and can postpone or eliminate the needs to two luxuriant chromium processing.

More basic is, the technical staff can use at least some embodiment of double function probe of the present invention, the measurement decoupling zero is shifted in induction and electric charge, thereby the mechanism to electrostatic charge and electrostatic charge generation and dissipation provides clearer understanding, has broken away from by bed electric capacity because the static noise that the localized variation of fluidisation and foaming causes.Expect that this understanding will bring and more clearly pay close attention to the Electrostatic Control technology, such as continuously auxiliary agent and antistatic additive.Second benefit is more clearly to have understood fluidisation and the foaming in the fluid bed.

Any output that may be used to process difunctional electrostatic probe of various signal processing technologies.For example, double function probe can be for generation of indicating the high-speed data that bubbles in the fluid bed, and determine that from high-speed data reactor wall and probe distal partly go up at least one electrical properties of coating (such as the naked probe of double function probe and the electrical properties of last minute coating of insulated probe).In some cases, frequency analysis can be used for (from the output of double function probe) and extracts because the induction composition that the variation of bubble by the localized capacitance that causes causes.In other cases, be used for the wavelet method of asynchronous signal analysis and/or the relative measurement that the short-term Fourier method can be used for extracting from the output of double function probe the charge density relevant with foaming.Not bubbling to indicate fluidisation bad (being similar to cold band), and it may be the tendency of knot sheet.

The coating that be monitored in certain embodiments, is not on the reactor beds wall.On the contrary, this coating during reaction is exposed to another surface upper (and on distal portions of the every electrostatic probe that adopts) of the fluidized bed reactor system of streaming flow during monitoring.For example, this coating can be the taking away on the surface in the district of reaction system (being the coating 11A on pipeline 11 inner surfaces of system among Fig. 1 such as this coating), and described supervision can adopt at least one electrostatic probe of placing in taking away the district to monitor the static (such as the probe 3 ' of Fig. 1 middle probe assembly 2 ') that shifts.In this linguistic context, the expression of fluidized bed reactor system " taking away the district " indicates any position of (being outside the fluid bed) outside the intensive phase region of this system in the fluidized-bed polymerization reactor system, and the expression of " transfer static " refers to take away the electrostatic charge that is produced by particulate (such as catalyst particles and resin particle) CONTACT WITH FRICTION (as to the metallic walls of gas recirculation pipeline or to taking away another parts in district) in the district.In this class embodiment, method of the present invention is carried out in fluidized-bed polymerization reactor during the polymerisation, uses at least one electrostatic probe to monitor that reactor takes away the coating on the distal portions of district's element and every electrostatic probe.In typical case, every electrostatic probe all is external probe, makes its distal portions and the relevant district's element leveling of taking away during installation, perhaps slightly extends to the streaming flow from such element.

In certain embodiments, use the method for at least one electrostatic probe to comprise to monitor the coating on the distal portions of reactor assembly surface (surface of taking away the district such as bed wall or the reactor of reactor) and every electrostatic probe in fluidized-bed polymerization reactor system (this paper is referred to as " reactor " sometimes) during the polymerisation, wherein this coating is exposed to the streaming flow in the reactor assembly during execution this method.In this class embodiment, this method may further comprise the steps:

(a) during in reactor, reacting, operate this electrostatic probe and produce a series of data values (this paper is referred to as " high-speed data " sometimes), indicate fluid flow variations during the very first time interval (as bubbling or turbulent flow); And

(b) determine (such as last minute coating of electrostatic probe distal portions) at least one electrical properties of this coating from high-speed data.

This paper introduction determine that from high-speed data any technology of the electrical properties of bed wall coating may be used to the high-speed data of more determining the embodiment of wide class from this, determine the electrical properties of (as taking away on the district's parts) coating beyond the bed wall coating.

High-speed data can comprise from about 1Hz to about 10Hz or from about 2Hz to about 6Hz scope in frequency component, and low-limit frequency reciprocal much longer in these frequency components of the Duration Ratio in the first interval.For example, if concerned lowest frequency components is 1Hz in the high-speed data, then the first interval can be at least one minute (such as a few minutes).(for every electrostatic probe) concerned frequency range is the frequency range of the signal of telecommunication responded in electrostatic probe for the mobile variation of electrostatic probe by fluid-phase between the stage of reaction.

At least one electrical properties of determining in step (b) can be the breakdown voltage of this coating.In some embodiment of wide class more, this method has also comprised following steps:

(c) pollution level of determining the degree of degeneration of this coating and this coating from least one electrical properties of determining step (b) is one at least.For example, step (c) can comprise that from the electrostatic probe distal portions of determining the breakdown voltage of coating determines the step of this coating degradation degree.In some embodiment of the more wide class of pointing out, during reaction step (a) and (b) (perhaps step (a), (b) and (c) whole) have been carried out in online mode.

In certain embodiments, this method has also comprised from least one electrical properties of determining step (b) and judges whether to add the continuous adding agent or increase the feed rate of adding the continuous adding agent to reactor to this reactor.This judgement can be undertaken by wall film controller, and it is obtained input (such as breakdown voltage or steady-state current value) and use this information control to the feed rate set-point of the continuous adding agent of reaction system interpolation from wall film monitor.For example, if that the electrical properties of measuring indicates the quality of biofilm formed on wall of reactor is bad, wall film controller will increase continuous adding agent flowing to reactor so.If it is good that the electrical properties of measuring indicates the quality of biofilm formed on wall of reactor, wall film controller will reduce or stop continuous adding agent flowing to reactor so.

This method also can comprise step (b) definite electrical properties and the step that compares with reference to breakdown voltage.If the electrical properties of determining is less than the reference breakdown voltage, continuous adding agent this method may further include to this reactor and adds the continuous adding agent or increase the speed of adding the continuous adding agent to reactor so.If the electrical properties of determining is greater than breakdown voltage, this method may further include and reduces the feed rate that the forward reaction device adds the continuous adding agent so, and/or stops to add the continuous adding agent to reactor.

In certain embodiments, indicate per two hours of bad wall membrane stage for wall film monitor, the speed of adding the continuous adding agent to reactor assembly can be increased 5% or 7% or 10% or 15%.

Some embodiment of this method adopts double function probe to produce high-speed data.Other embodiment adopt other electrostatic probes to produce high-speed datas (as 6,008,662 and 6,905, introduce the routine intravenous electric probe of type in No. 654 United States Patent (USP)s).

Next step introduction of this paper be can be monitored and the also alternatively commercial-scale reaction of control (such as commercial size gas fluidised bed polymerisation reaction) example.Some such reaction can be in having Fig. 1 occurs in the reactor of the geometry of reactor 4.Different embodiment according to the subject invention can monitor operation any in various different reactor.

In certain embodiments, at continuous gas-phase fluidized-bed reactor for monitored when carrying out polymerization and move and also control alternatively as follows; Fluid bed is comprised of polymer beads.The gaseous state feed flow of original monomer and hydrogen is mixed together in the hybrid tee device with liquid or gaseous comonomers, and is being introduced in recycle gas pipeline under the reactor beds.For example, original monomer is ethene and comonomer is the 1-hexene.The controlled gas composition target to keep fixing of each flow velocity of ethene, hydrogen and comonomer.The concentration of ethene is controlled to keep constant ethylene partial pressure.Hydrogen is controlled to keep constant hydrogen to ethylene molar ratio.Hexene is controlled to keep constant hexene to ethylene molar ratio (perhaps as an alternative, the flow velocity of comonomer and ethene is maintained at fixed proportion).The concentration of all gas is all measured by online gas chromatograph, and is relatively constant to guarantee the component in the stream of recycled gases.Use the nitrogen that purifies as carrier solid or liquid catalyst directly to be injected in the fluid bed.Adjust the feed rate of catalyst to keep constant productivity ratio.By the continuous-flow of supplying feeding and recycle gas by reaction zone (being fluid bed), the reaction bed of growth polymer beads is held fluidized state.

In some is implemented, use 2.0 to 2.8ft/sec superficial gas velocity for realizing this situation, and this reactor is with the gross pressure operation of 300psig.In order to keep constant temperature of reactor, the temperature of recycle gas is adjusted up and down to adapt to any variation that causes rate of heat generation owing to polymerization continuously.By taking out part bed with the speed that equates with grain products formation speed, fluid bed is maintained at constant height.This product semi-continuously is removed to via a series of valves in the chamber of fixed volume, and it is drained back reactor simultaneously.This just allows the efficient removal of this product, and simultaneously most unreacted gas recirculation is returned reactor.This product is cleaned to remove that carry secretly and hydrocarbon dissolving, and with a small amount of being processed by moistening nitrogen so that any traces of residual catalysqt deactivation.

In other embodiments, reactor move to use various different process (such as slurries or gas phase process) any monitored and also controlled alternatively when carrying out polymerization.For example, this reactor can be fluidized-bed reactor, moves to produce polyolefin polymer by gas-phase polymerization process.The method of the reactor that such reactor and operation are such is well-known.Carry out the in service of gas-phase polymerization process at such reactor, can mechanically stir or the fluidisation polymerisation medium by the continuous-flow of gaseous monomer and diluent.

In some was implemented, monitoring and also controlling alternatively was the polymerisation of continuous gas phase process (such as fluidized-bed process).Comprise in typical case reaction zone and Speed Reduction district (being also referred to as expanding part) for the fluidized-bed reactor of carrying out this technique.Reaction zone comprises the bed of growth polymerization composition granule, by the polymer beads that forms of the continuous-flow fluidisation of the gas reactor by reaction zone and the catalyst granules of trace.Optionally, the gas of some recirculation can be cooled and compress to form liquid, and this has promoted the heat abstraction ability when circulating current is recaptured into reaction zone.This method of operating is called as " condensation mode ".The airflow rate that is fit to can easily be determined by simple test.The speed of gaseous monomer, comonomer and the hydrogen that circulating current is supplied equals the speed that microparticle polymer product and monomer associated with it are removed from reactor, in order to keep in the reaction zone the in essence gas composition of stable state.The gas that leaves reaction zone is passed to the Speed Reduction district, and the particle of here carrying secretly is removed.In cyclone separator and/or fine filtrator, can remove thinner entrained particles and powder.Gas compresses in compressor and by heat exchanger, has removed therein the heat of polymerization, then turns back to reaction zone.

Given viscosity or the sintering feature of polymer in the fluid bed, the temperature of reactor of fluidized-bed process (Trx) is usually with feasible maximum temperature operation, in order to make the maximization of heat abstraction ability.

According to some embodiment that this paper introduces, reaction monitored and that also control alternatively can produce the homopolymers (such as the homopolymers of ethene) of alkene, and/or the alkene especially copolymer, terpolymer etc. of ethene and at least a other alkene.Described alkene for example can comprise 2 to 16 carbon atoms; Perhaps comprise from 3 to 12, perhaps comonomer and the ethene of 4 to 10 or 4 to 8 carbon atoms.Polyethylene is produced in reaction monitored and that also control alternatively.Such polyethylene can be the homopolymers of ethene and the interpretation of ethene and at least a alpha-olefin, and therein ethylene content is about at least 50% of the total monomer weight that relates to.Utilizable demonstration alkene is ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-laurylene, 1-hexadecylene etc. in embodiments of the present invention.This paper is same available to be polyenoid, such as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, bicyclopentadiene, 4-vinyl-1-cyclohexene, 1,5-cyclo-octadiene, 5-ethenylidene-2-ENB and 5-vinyl-2-ENB, and the alkene that in polymerisation medium, forms in the original place.When the alkene in original place formation in polymerisation medium, the polyolefin that can comprise long chain branches forms.

In polyethylene or polyacrylic production, in polymer reactor, may there be one or more comonomers.When existing, comonomer can exist will realize any other ethene of level or propylene monomer that the percentage by weight that comonomer is desired merges in the resin of finishing.In an embodiment of polyethylene production, comonomer follows ethene to exist, the scope of the molar ratio of gas phase from 0.0001 (comonomer: ethene) to 50, perhaps from 0.0001 to 5, perhaps from 0.0005 to 1.0, perhaps from 0.001 to 0.5.Represent that with absolute term when making polyethylene, the scope of the ethene amount that exists can be as high as 1000 atmospheric pressure in polymer reactor, perhaps high to 500 atmospheric pressure, perhaps high to 100 atmospheric pressure, perhaps high to 50 atmospheric pressure, perhaps high to 10 atmospheric pressure.

In olefinic polymerization, often use hydrogen to control polyolefinic final character.For the antigravity system of some type, known raising hydrogen concentration (or dividing potential drop) has reduced molecular wt, and has improved the polyolefinic melt index (MI) that produces.Thereby this MI can be subject to the hydrogen concentration impact.Amounts of hydrogen when polymerization can be represented as the molar ratio with respect to the main polymerisable monomer that exists in reactor; For example, ethene or propylene.The amounts of hydrogen of using in some polymerization technique is to realize expectation MI(or the molecular wt of final vistanex) necessary amount.In one embodiment, hydrogen is to the gas phase molar ratio (H of total monomer ₂: monomer) greater than 0.00001, perhaps greater than 0.0005, perhaps greater than 0.001, perhaps less than 10, perhaps less than 5, perhaps less than 3, perhaps less than 0.10, the scope that wherein can expect can comprise any molar ratio upper limit that this paper introduces and any combination of any molar ratio lower limit.In another way expression, the scope of the amounts of hydrogen in the reactor can be as high as 10ppm at any time, and is perhaps high to 100ppm, perhaps 3000ppm, perhaps 4000ppm, perhaps 5000ppm, perhaps between 10ppm and 5000ppm, perhaps between 100ppm and 2000ppm.

According to the embodiment of this paper introduction monitored and also alternatively controlled reactor can be the element that adopts the grading reactor of two or more tandem reactors, one of them reactor can be produced for example macromolecule weight component, and another reactor can be produced low molecular wt component.

Monitored and also alternatively controlled reactor can exist at the antigravity system of metallocene or metallocene type and not exist or in fact without any cleanser, carry out slurries or gas phase process during such as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and three-n-hexyl aluminium and diethyl aluminum chloride, diethyl zinc etc.So-called " not having in fact ", it means that these compounds are not added to reactor or any reactor parts wittingly, and if exist, the existence in reactor is also less than 1ppm.

Monitored reactor can adopt one or more catalyst, with the static of " continuous adding agent " or other " antistatic additive " combination with the control reactor, as what introduce in U.S. Patent Application Publication No. 2005/0148742.In certain embodiments, the continuous adding agent is metal fatty acid compound (such as aluminum stearate), and it is fed into reactor with the amount (based on polymer production rate) up to 50ppm.In other embodiments, the continuous adding agent can be antistatic additive, and such as ethoxylated amine or first amine oxide, the example is Kemamine AS-990(ICI Specialties, Bloomington Delaware) (perhaps its combination).Other antistatic components comprise Octastat compounds of group, Octastat2000,3000 and 5000 or rather.Other embodiment can comprise the combination of fatty acid metal and antistatic compound, based on the amount of polymer production rate height to 100ppm.

According to the monitored of certain embodiments of the invention with also alternatively in the controlled reactor, loaded catalyst can with the continuous adding agent combination up to 6wt%, then introduce reactor.For example, up to the aluminum stearate of 3.0wt% and up to the ethoxylated amine of 2.0wt% can with catalyst combination, then introduce reactor.Add the continuous adding agent by cylinder and/or other devices that is fit to catalyst.

In other embodiments, metal fatty acid compound and/or antistatic additive are added to reactor as one or more feeding material that separate; For example, as the slurries of the additive in the hydrocarbon diluent or antistatic additive, as the solution in the hydrocarbon diluent, perhaps as the direct feeding material (being preferably powder) of solid granulates.An advantage of this adding method is the feed rate that it allows to adjust additive onlinely, and is irrelevant with the speed of catalyst feeding.In other embodiments, the continuous adding agent is added to recirculation line.

The example of the polymer that can produce comprises the following: C ₂-C ₁₈The homopolymers of alhpa olefin and copolymer; Polyvinyl chloride, EPM (EPR); Ethylene propylene diene rubber (EPDM); Polyisoprene; Polystyrene; Polybutadiene; The polymer of butadiene and styrene copolymerisation; The polymer that butadiene and isoprene copolymer close; The polymer of butadiene and acrylonitrile; The polymer that isobutene and isoprene copolymer close; Ethylene butene rubber and ethylene butene diene rubber; And polychloroprene; With one or more C ₂-C ₁₈ENB homopolymers and the copolymer of alhpa olefin; One or more C with alkadienes ₂-C ₁₈The terpolymer of alhpa olefin.

Comprise one or more of the following: C at monomer monitored and that also can exist in the controlled reactor alternatively ₂-C ₁₈Alhpa olefin, such as ethene, propylene, and at least one diene alternatively, for example, hexadiene, bicyclopentadiene, comprise octadiene, norbornadiene and the ethylidene norbornene of methyl octadiene (such as the 1-methyl isophthalic acid, 6-octadiene and 7-methyl isophthalic acid, 6-octadiene); And the monomer that condenses easily, for example, isoprene, styrene, butadiene, isobutene, chlorobutadiene, acrylonitrile, cyclenes are such as ENB.

According to some embodiment of the present invention, fluidised bed polymerisation can be monitored and be also controlled alternatively.Reaction can be the fluidized polymerization reaction of any type, and can carry out in single reactor or multiple reactor, such as the reactor of two or more series connection.

In a plurality of embodiment, many dissimilar polymerization catalysts any can both be used in monitored and also alternatively in the controlled polymerization process.Can use single catalyst, also can when expectation, adopt the mixture of catalyst.This catalyst can be for soluble or insoluble, support type or non-loaded type.It can be prepolymer, to have or without spraying, slurries/suspension or the dispersion of filler, liquid or solution drying.These catalyst can be with well-known co-catalyst and auxiliary agent use in the industry.Co-catalyst and auxiliary agent can comprise alkyl aluminum, aluminum alkyl halide, alkyl aluminum hydride and aluminum alkoxide in typical case.Just to showing purpose, the example of the catalyst that is fit to comprises Ziegler-Natta catalyst, chromium-based catalysts, catalytic component based on vanadium (such as vanadium oxytrichloride and vanadium acetylacetonate), metalloscene catalyst and other single centers or single center type catalyst and constrained geometry configuration catalyst, the metal halide of cationic form (such as aluminum trihalide), the initator of anion (such as butyl lithium), Co catalysts and composition thereof, Raney nickel and composition thereof, iron catalyst and composition thereof, rare-earth metal catalyst (those of metal that namely contain periodic table Atom ordinal number 57 to 103) is such as cerium, lanthanum, praseodymium, the compound of gadolinium and neodymium.

In a plurality of embodiment, monitored and also alternatively controlled polymerisation can adopt other additives, such as (for example) inert particulate particle.

The wall film controller of this paper introduction allows to determine for the insulating property (properties) of recovering biofilm formed on wall of reactor the continuous adding agent of the correct amount that need to add to reactor.Although the accurate amount of needed continuous adding agent may change with the catalyst that just is being used, polyethylene grade (such as MI and density targets), throughput rate and the reactor conditions of making, but wall film controller allows the reactor operator to add enough continuous adding agent to reaction system, to recover the insulating property (properties) of biofilm formed on wall of reactor, the continuous adding agent may be minimized any deactivation that catalyst has.

For example, the operability problem in the fluidized-bed reactor is in typical case because the impurity (as from raw material) in the reactor is perhaps bad because of the wall film quality.In typical case, the reactor operator will respond the operability problem, add the continuous adding agent of certain tittle.There is not wall film controller, the reactor operator just may add too much continuous adding agent, cause catalysqt deactivation, cause the too much continuous problem of taking away electrostatic charge and continuing, thereby so that the reactor operator concludes that it is necessary that two expensive and time-consuming luxuriant chromium are processed.As an alternative, do not have wall film controller, the reactor operator just may add continuous adding agent very little, and it is bad to cause the reactor operability to continue, thereby so that the reactor operator concludes that it is necessary that two expensive and time-consuming luxuriant chromium are processed.But, even in both cases after two luxuriant chromium are processed, all still may exist the operability problem of reactor because the origin of operability problem be because impurity rather than since static carry secretly.Whether use the reactor wall controller will allow the reactor operator to judge at the very start this operability problem because static is carried secretly and wall film quality bad (thereby be owing to another kind of reason during such as impurity, potentially to avoid expensive and time-consuming two luxuriant chromium processing in the operability problem).Use the reactor wall controller also will to allow the reactor operator to add in order to recover the continuous adding agent of the needed correct amount of reactor steel surface upper wall film insulating barrier, thereby prevented the electrostatic charge of resin and catalyst.

The method of this paper introduction can comprise that at least one electrostatic probe that uses in the fluidized bed reactor system monitors coating, comprise on the surface of described reactor assembly and the polymer film of the distal portions of every described electrostatic probe, wherein said coating is exposed to described intrasystem streaming flow.Described supervision can may further comprise the steps: (i) during the very first time interval between the stage of reaction described in the described reactor assembly, operate described electrostatic probe and produce high-speed data and indicate foaming in the described fluid bed; And at least one electrical properties of (ii) determining described coating from described high-speed data.Under the preferable case, the electrical properties of this coating is the breakdown voltage of biofilm formed on wall of reactor.In case just being determined, the electrical properties of this coating the reference breakdown voltage of itself and this coating can be compared.

The breakdown voltage of biofilm formed on wall of reactor may be subject to the impurity effect that exists in film thickness and the film.The melt index of wall film and density also may affect the breakdown voltage of this film.Degenerate and become contaminated along with the wall film, it has just lost its insulating property (properties) and has begun to act as conductor according to ohm law.The reference breakdown voltage of wall film is the point that the wall film begins to act as conductor and satisfies ohm law by the electric current of wall film along with the voltage linear increase of striding the wall film.For example, be about 50 for polyethylene known reference breakdown voltage, 000V/mm.Therefore be approximately the wall membrane coat of 1/4mill for thickness, the breakdown voltage of this film is about 0.3kV.

Then the electrical properties of determining from high-speed data compares with the reference breakdown voltage of this coating.If electrical properties less than the reference breakdown voltage of coating, is then added continuous adding agent a period of time to polymer reactor, until the coating electrical properties of determining is more than or equal to the reference breakdown voltage of coating.For example, can add the continuous adding agent to reactor with the speed more than or equal to 5ppm, 10ppm or 15ppm.For example, can be increased 5% or 7% or 10% or 15% in a period of time to the speed that reactor adds the continuous adding agent, until new electrical properties is more than or equal to the reference breakdown voltage of coating.

If there is not one theory, think that the continuous adding agent has promoted polyethylene film in the lip-deep deposition of steel reactor wall.For example, think that common continuous adding agent (such as aluminum stearate) has polarization and non-polarized function.Function of polarization is considered to preferentially stick/be attached to the exposing metal surface (being the wall position that the wall film is degenerated) of reactor wall, thereby helps polyethylene particle preferential deposition and additional wall film.

If there is not one theory, think that the polymerisation that wall film controller that this paper introduces moves when having induced condensing agent is particularly useful.Think that the condensing agent of long-term use lifting capacity can cause the infringement to two luxuriant chromium polymer insulation layer on the reactor wall.The wall film controller of this paper introduction can be used in the infringement that alleviates the wall film, and mode need not be processed by two luxuriant chromium for repairing the insulation wall film.

Example

In example, commercial-scale gas-phase fluidized-bed polyethylene reactor operates under the condensation mode with metalloscene catalyst, forms the LLDPE of several grades.Typical running status provides in table 1.

Table 1. is without the state of the art of the example run duration of continuous auxiliary agent.

?	Mean value	Standard deviation
			CofeedPPM	0.0	0.00
Throughput rate (klb/hr)	112.7	12.10
			Reactor pressure (psig)	290.0	0.76
Temperature of reactor (F)	184.0	1.71
			Reactor Δ T (F)	69.3	6.07
Superficial gas velocity (ft/s)	2.4	0.04
			Fluid bed liquid level (ft)	46.5	0.31
Reactor hydrogen concentration (ppm)	191.9	19.53
			Reactor ethylene partial pressure (psia)	205.6	3.75
Reactor C6/C2 concentration ratio	2.1	0.16
			Reactor iC5 concentration (pct)	16.7	1.25
Reactor dew point (F)	159.6	5.18
			The percentage by weight of condensation	23.7	3.28
Inlet temperature (F)	114.7	5.35

During reaction, be positioned at the electrostatic probe at the above 3.5 feet places of dispenser panel for electric current and the voltage of measuring the wall film.As seen in fig. 6, the A section indicates the wall film from the measurement result of probe and just moves as insulator in essence.Along with passage of time, indicate little by little lower voltage and electric current increases from the measurement result of this probe.Along with the continuation of reaction, the reactor wall state degenerates to so that the point that wall knot sheet and the excessive compulsive reaction device of the dirt that hardens are closed.Can see this situation in the B of Fig. 6 section, wherein the measurement result from probe indicates the wall film with the conduction state operation, has 450 volts corresponding low breakdown voltage.

Then added continuous auxiliary agent to reactor, the typical running status that provides in the table 2 has been provided.The continuous auxiliary agent that uses is the mixture of aluminum stearate and ethoxyquin Stearyl Amine.As A section finding in Fig. 7, after introducing continuous auxiliary agent, the probe measurement result indicates wall film breakdown voltage and has returned to about 1700V.Recovered good reactor operational capacity, knot sheet or startup fouling excessively almost do not have.

Table 2. has the state of the art of the example run duration of continuous auxiliary agent.

?	Average	Standard deviation
			CofeedPPM	5.4	1.03
Throughput rate (klb/hr)	91.5	9.24
			Reactor pressure (psig)	290.0	0.73
Temperature of reactor (F)	182.0	2.36
			Reactor Δ T (F)	66.8	4.98
Superficial gas velocity (ft/s)	2.4	0.03
			Fluid bed liquid level (ft)	46.9	0.28
Reactor hydrogen concentration (ppm)	289.9	76.27
			Reactor ethylene partial pressure (psia)	198.1	5.18
Reactor C6/C2 concentration ratio	2.3	0.13
			Reactor iC5 concentration (pct)	14.2	1.37
Reactor dew point (F)	151.4	5.83
			The percentage by weight of condensation	17.9	2.41
Inlet temperature (F)	115.2	4.51

After the good operation of a period of time, reactor is closed to remove the dirt that hardens that has formed at the early stage run duration that does not have continuous auxiliary agent.Startup subsequently and steady-state operation can restart with good reactor operation, and lasting some months.

Although should be appreciated that together with some specific embodiments of the present invention and case introduction it, above explanation is intended to show rather than limit the scope of the invention.Other aspects, advantage and modification will be apparent for the technical staff in the field under the present invention.

Unless stipulate in addition, phrase " comprises " in essence and " just comprising in essence " do not got rid of and have other steps, element or material, no matter whether state specially in this manual, as long as such step, element or material do not affect the present invention basic with feature novelty, in addition, they do not get rid of the impurity related with the element that uses and material normal phase.

For the purpose of concise and to the point, only some scope discloses in this article clearly.But, can be combined with any upper limit to state not the clearly scope of statement from the scope of any lower limit, and from the scope of any lower limit can be combined with any other lower limit with the statement not clearly the statement scope, in the same way, can be combined with any other upper limit to state not the clearly scope of statement from the scope of any upper limit.

Whole documents that this paper quotes are quoted whole authorities of being allowed to and are quoted as a reference fully to so open degree consistent with explanation of the present invention for such.

Claims

1. the method for an olefin polymerization comprises:

(a) during polymerisation, use at least one electrostatic probe in the fluidized bed reactor system to monitor coating, described coating comprises the distal portions of every described electrostatic probe and the lip-deep polymer film of described reactor assembly, wherein said coating is exposed to described intrasystem streaming flow, and described supervision may further comprise the steps:

(i) during the very first time interval between the stage of reaction described in the described reactor assembly, operate described electrostatic probe indicates the foaming in the described fluid bed with generation high-speed data; And

(ii) determine at least one electrical properties of described coating from described high-speed data;

(b) the described electrical properties that will in step (a), determine and the contrast of the reference breakdown voltage of described coating; And

(c) if described with reference to breakdown voltage less than described coating of described electrical properties, then increase continuous adding agent a period of time to polymer reactor, until described with reference to breakdown voltage more than or equal to described coating of described definite electrical properties of described coating.

2. according to claim 1 method, wherein, the described surface of described reactor assembly is a wall, and described coating is exposed to streaming flow in the described fluid bed between the described stage of reaction.

3. according to claim 1 and 2 method, wherein, described coating is polymer film.

4. any one method according to claim 1-3, wherein, the frequency component in described high-speed data comprises from about 1Hz to about 10Hz scope, and described the first interval is at least one minute perdurabgility.

5. according to claim 4 method, wherein, by with the sample frequency of 100Hz at least the output sampling of described electrostatic probe being produced described high-speed data.

6. according to claim 4 method, wherein, described coating is thickness less than 0.50 millimeter polymer film.

7. any one method according to claim 1-6, wherein, at least one described electrical properties is the breakdown voltage of described coating.

8. any one method according to claim 1-7, wherein, described very first time interval comprises the subinterval group, described high-speed data indicates during described each subinterval in described the first interval, owing to the electric current of in described probe, being responded to by electric charge in the described fluid bed, by the mean power of described probe extraction, and step (a) (ii) may further comprise the steps:

Determine the current potential the described fluid bed during described each subinterval in described the first interval from described high-speed data.

9. any one method according to claim 1-7, wherein, described very first time interval comprises the subinterval group, and step (a) (ii) may further comprise the steps:

By the cross-correlation of the described high-speed data that produces in one of version after the processing of the described high-speed data that produces in the described high-speed data described each subinterval in described the first interval being determined produce in the described subinterval and the described subinterval and the described subinterval, determine cross correlation value; And

Determine the current potential the described fluid bed during described each subinterval in described the first interval from described high-speed data and described cross correlation value.

10. according to claim 9 method, wherein, described cross correlation value indicates described bubbles in fluidized by the motion of described electrostatic probe.

11. any one method according to claim 1-10, wherein, described electrostatic probe is difunctional electrostatic probe, comprising:

The probe of insulation has the distal portions of electric insulation that is exposed to the part coating of described streaming flow with described coating during step (a), with the proximal part of the conduction that contacts with described distal portions; And

The naked probe of conduction is arranged coaxially with the probe of described insulation, and has the distal surface of conduction that is exposed to another part coating of described streaming flow with described coating during step (a).

12. any one method according to claim 1-11, wherein, the described of described coating is that described coating begins the point that increases along with the voltage linear of striding described coating as conductor and the electric current by described coating with reference to breakdown voltage.

13. any one method according to claim 1-12, wherein, the continuous adding agent can be by adding described reactor to more than or equal to the speed of 5ppm.

14. method according to claim 13, wherein, the continuous adding dosage that adds described reactor to every two hours increases by 5%, until described with reference to breakdown voltage more than or equal to described coating of the electrical properties of measuring.